Systemic activity of simeconazole and its derivatives in plants

The systemic activity of simeconazole (RS-2-(4-fluorophenyl)-1-(1H-1,2,4-triazol-1-yl)-3-trimethylsilylpropan-2-ol) and a number of its derivatives in plants has been investigated to establish which portion of the structure of the molecule contributes to this outstanding activity. The results revealed that the hydroxyl group of the simeconazole moiety is essential for vapour-phase activity and translocation from roots of the compound. They showed that the presence of a fluorine atom in the structure was not indispensable for vapour-phase activity or translocation from roots, although the fluorine atom contributed to these systemic movements. In addition, it was found that the fungicidal activity of simeconazole against Rhizoctonia solani Kühn and Blumeria graminis DC fsp hordei Marchal is potentiated by the fluorine atom, since the activity of a compound which lacked fluorine in the 4-position of the phenyl ring was inferior to that of simeconazole. A compound in which the silicon atom of simeconazole was replaced by a carbon atom showed lower antifungal activity than simeconazole, while phytotoxicity was caused in rice plants by soil drench of the compound. Therefore, the silicon atom of simeconazole may contribute to its selectivity between fungi and plants.     

The persistence of insecticide spray deposits on woven polypropylene and jute sacking

In a trial, simulating the spray treatment of bags, the persistence and biological activity of insecticide spray deposits on jute and woven polypropylene sheets have been compared; in addition, the build-up of residues in thin layers of maize under the sprayed sheets has been measured. The insecticides were found to have a much shorter persistence on polypropylene than on jute and this was coupled with higher residues on the grain. However, the deposits on polypropylene retained equal or greater activity against Sitophilus zeamais Motsch. and Tribolium castaneum (Herbst) than the deposits on jute, despite the loss of surface deposit. Wettable powder formulations had a slightly greater surface persistence than emulsifiable concentrates and resulted in smaller residues in the grain. There would seem to be more usefulness in using insecticide sprays on woven polypropylene than on jute bags, and a wettable powder formulation of a non-volatile insecticide of low mammalian toxicity would be the best choice. Of the insecticides tested, the pyrethroid permethrin (cis: trans ratio= 25:75) was the most effective and gave the least residue in the grain.     

靶标酶在研究杀虫活性构效关系中的应用

运用已建立的乙酰胆碱酯酶(AChE) 活力分析规范化筛选模型, 研究N-甲基取代苯基氨基甲酸酯类化合物和含硅氨基甲酸酯类新系列化合物与AChE 酶抑制中量( I50)构效关系的规律, 并以CA SAR 软件进行Q SAR 分析, 所得结果迅速反馈给化学合成, 为高效低毒新杀虫剂的创制提供有益的信息和科学依据。     

O-ethyl O-isopropyl O-(5-methoxy-1-methyl-6-oxo-1H-pyridazin-4-yl) phosphorothioate,a new experimental insecticide and acaricide

The insecticidal and acaricidal action, anti-cholinesterase activity and toxicity to rats of a new experimental pesticide, O-ethyl O-isopropyl O-(5-methoxy-1-methyl-6-oxo-1H-pyridazin-4-yl) phosphorothioate ( I ), and those of some by-products found in the technical material, are described. High insecticidal and acaricidal effectiveness of I was found in laboratory and field trials. The activity as a soil insecticide in field trials was equal to, or greater than, that of other chemicals used at present.     

季铵盐和有机硅助剂对啶虫脒杀虫活性及水生生物毒性的影响

分别以浸渍法和相加指数法,评价了5种季铵盐助剂和3种有机硅助剂分别与啶虫脒混合使用时对苹果黄蚜Aphis citricola的联合作用,以及对两种非靶标水生环境生物大型溞Daphnia magna和斑马鱼Brachydonio rerio的毒性。结果表明,有机硅助剂和季铵盐助剂对啶虫脒防治蚜虫具有明显的增效作用,且silwet 618的增效倍数高达210.2。环境毒性试验结果表明:啶虫脒对两种水生生物均为低毒;供试季铵盐和有机硅助剂对大型溞的单一毒性均为剧毒,季铵盐助剂对斑马鱼为高毒,而有机硅助剂对斑马鱼为中毒。与农药联合作用测定结果表明:有机硅助剂对两种水生生物均表现为增毒作用;而5种季铵盐助剂除十四烷基二甲基苄基氯化铵（1427）对大型溞表现为增毒作用外,其他4种对两种水生生物均呈现不同程度的拮抗作用。此外,季铵盐和有机硅助剂还可以显著降低清水的表面张力（由清水的74.37 mN/m降为20.50~40.07 mN/m）,提高叶片上的最大持留量（由清水的1.54 μg/cm2提高到2.39~4.34 μg/cm2）。因此,使用季铵盐和有机硅助剂作为增效剂时应考虑其对水生生物的毒性,其中季铵盐助剂对环境生物的潜在威胁更小。     

Organosilane insecticides. Part I: Biological and physical effects of isosteric replacement of silicon for carbon in etofenprox and MTI-800

Substitution of silicon for carbon was explored in etofenprox and MTI-800, primarily to establish the suitability of silicon for pesticide construction and to probe steric effects. It was shown that silicon is an effective building block for insecticides with subtle qualitative and quantitative differences relative to the carbon analogs. The silanes were slightly less toxic to insects than the carbon analogs (relative potency of 0.2-0.6) but the silane analog of MTI-800 was considerably less toxic to fish (0% mortality at ≥50 mg liter^?1) than MTI-800 itself (LC₅₀ = 3 mg liter^?1). The mode of action of both carbon and silicon compounds was similar in the intact, electrode-implanted cockroach and involved repetitive firing of a sensory nerve; potency measurements were also made using an in-vitro nerve assay. The possible metabolic and physicochemical contributions to the observed insecticide potencies were explored using synergism studies, physical chemistry measurements and quantum mechanical calculations.     

New melanin biosynthesis inhibitors and their structural similarities

Relationships between their activities as blast control agents, and their abilities to inhibit mycelial melanisation on a nutrient agar, are described for 103 substituted benzothiazol-2(3H)-ones, benzoxazol-2(3H)-ones, indolin-2-ones, quinolin-2(1H)-ones, 1,2,3,4-tetrahydroquinolin-2-ones, benzo-1,4-thiazin-3(2H)-ones and benz-1,4-oxazin-3(2H)-ones, and some corresponding thiones. Several compounds in the respective series had a high protective activity and an antimelanisation activity against the blast fungus Pyricularia oryzae; furthermore, there was a good correlation in both of these activities, indicating that these compounds belong to the group of melanin biosynthesis inhibitors. Structural similarities of these compounds can be identified as follows: (a) having a benzo-bicyclic ring system; (b) containing a nitrogen atom in one ring at a position alpha to the benzene ring system; and (c) substitution, at the ring nitrogen atom, at the peri position in the aromatic ring relative to the nitrogen atom, and at the position alpha to the nitrogen atom in the ring system, with a double bond such as in carbonyl and thiocarbonyl groups. Among the compounds that have been proposed as melanin biosynthesis inhibitors, the chemical structures of tricyclazole, pyroquilon, 4,5-dihydro-4-methyltetrazolo[1,5-a]quinazolin-5-one (PP-389), [1,2,4]-triazolo[4,3-a]quinoline and 1-methylquinolin-2(1H)-one exhibit the structural similarities described above; however, 4,5,6,7-tetrachlorophthalide, 2,3,4,5,6-pentachlorobenzyl alcohol and N-substituted-2,3,4,5-tetrachloro-6-(hydroxymethyl)benzamides do not have such similarities in their chemical structures.     

Toxicity of ddt and malathion to various larval stages of Mamestra brassicae L.

The toxicity of DDT and malathion to the larvae of Mamestra brassicae was determined following several methods of application. The toxicity (LD₅₀), expressed as μg insecticide per g of insect, did not change significantly between larval instars (a) when either insecticide was injected into fourth to sixth instars; (b) when DDT was applied in the food of fifth and sixth instars; or (c) when malathion was applied topically to second to sixth instars. Significant changes in toxicity were found between successive instars when DDT was applied topically, but there was no clear trend. When malathion was applied in the food, the fifth instars were more susceptible than the sixth instars; it was found that the former consumed a toxic dose of malathion at a greater rate, and that probably malathion was degraded in the gut at a slower rate. In a contact test, the first to third instars were far more susceptible than the later instars to malathion; with DDT this trend was much less marked. Uptake studies with [¹⁴C]malathion showed that differences in the contact toxicity of malathion between instars could be explained, at least partly, by the decline in uptake per unit weight with increasing larval size.     

The kinetics of insecticide action. Part II: The relationship between the pharmacokinetics of substituted benzyl (1RS)-cis,trans-chrysanthemates and their relative toxicities to mustard beetles (Phaedon cochleariae fab.)

A mathematical model describing insect pharmacokinetics has been applied to data describing the penetration and elimination of a series of pyrethroid analogues [the methylbenzyl (1 RS)-cis, trans-chrysanthemates], applied to mustard beetles. The three parameters of the model (k_p, k_e and λ) have been estimated for each compound. The influence of chemical structure on pharmacokinetics, investigated using canonical correlation analysis, is discussed in relation to relative toxicity and knockdown action. In general, physicochemical properties which result in a slow flow of insecticide through the insect are associated with high toxicity. A large proportion (84%) of the variation in relative toxicity has been explained by resistance to elimination (1/k_e), implying that exposure of the site of action to insecticide is related to the total integral IM₂ for material (M₂) inside the insect. The remaining variation has been attributed to differences in behaviour at receptor sites. An optimum partition value (Δπ₀ ≈ 1.6) seems necessary for maximum pharmacodynamic activity in this series of compounds.     

The toxicity of mixtures of a pyrethroid with organophosphorus insecticides to Tetranychus urticae Koch

Laboratory studies of the cotoxicity of a pyrethroid insecticide, fenvalerate, and several organophosphorus insecticides against the two-spotted spider mite, Tetranychus urticae Koch, showed that a useful degree of potientation of toxicity occurred. The most effective combination of fenvalerate and azinphos-methyl was found to be a 1:1 ratio. Phosphates and phosphorodithioates in combination with fenvalerate were more toxic than phosphoromonothioates. The results suggest a practical method of improving the acaricidal activity of pyrethroid insecticides.     

The antifungal activity of alkyl benzimidazol-2-ylcarbamates and related compounds

The fungistatic activity against Penicillium digitatum and Diplodia natalensis decreased slightly in ascending a homologous series of alkyl esters of benzimidazol-2-ylcarbamic acid from the methyl ester (carbendazim) to the pentyl ester; the hexyl and octyl esters were inactive. 2-(Acylamino)benzimidazoles were slightly less active than the analogous alkyl benzimidazol-2-ylcarbamates. Introduction of a methylene bridge between the benzimidazole ring and the 2-methoxycarbonylamino group abolished antifungal activity. Methylation of either the carbamate nitrogen or an imidazole nitrogen of carbendazim produced inactive compounds. Replacement of the benzimidazole ring of carbendazim with various other ring systems was accompanied by marked reduction in antifungal activity.     

Effects of anti-ecdysteroid azole analogues of metyrapone on the larval development of the fleshfly,Neobellieria bullata

Based on our previous finding that PIM (phenyl-imidazolyl-metyra-pon; 2-(1-imidazolyl)-2-methyl-1-phenylpropan-1-one, 1) is a strong inhibitor of ecdysone 20-monooxygenase (IC₅₀ = 7.89 × 10^?7 M) from the fleshfly, Neobellieria bullata (Parker) and has also a good toxic action in vivo against this insect, 17 imidazole and 1,2,4-triazole analogues of metyrapone were synthesized and evaluated for their action against N. bullata larvae in terms of toxicity, length of larval development, weight of the puparium as well as special symptoms, i.e. malformations of the anterior and posterior spiracles, and of the mandibles. The introduction of p-methoxy (LC₅₀ = 49 mg kg^?1 in diet) or p-chloro (LC₅₀ = 97 mg kg^?1) substituents on the benzene ring of PIM resulted in a significant increase in toxicity compared to that of metyrapone (LC₅₀ = 561 mg kg^?1) and PIM (LC₅₀ = 148 mg kg^?1). The hybridization state of the carbon atom adjacent to the benzene ring was not an important factor for toxicity because the acetoxy derivative ( 13 ) was almost as toxic as PIM. At least one methyl group was required on the carbon atom adjacent to the azole ring to maintain activity, while an ethyl group ( 4 ) enhanced the toxic effect. At the applied doses some compounds including metyrapone itself, extended the duration of the larval development. Only metyrapone and PIM decreased the puparium weight. Several derivatives induced lethal malformations of mandibles as well as the anterior and posterior spiracles.     

Effect of dihydrodillapiole on pyrethroid resistance associated esterase inhibition in an Indian population of Spodoptera litura (Fabricius)

Resistance in Spodoptera litura (Fabricius) has been attributed to enhanced detoxification of insecticides by increased levels of esterases, oxidases and/or glutathione S-transferases. Enzyme inhibiting insecticide synergists can be employed to counter increased levels of such enzymes in S. litura. Dihydrodillapiole induced synergism of pyrethroid toxicity was examined in the laboratory-reared third instar larval population of S. litura collected in Delhi (susceptible), and Guntur (resistant) region of Andhra Pradesh, India. The Guntur population was found to be 7.04 and 10.19 times resistant to cypermethrin and lambdacyhalothrin, respectively. The activity of cypermethrin, lambdacyhalothrin and profenophos against susceptible and resistance populations of S. litura, was gradually increased when used along with a plant-derived insecticide synergist dihydrodillapiole. The α-naphthyl acetate hydrolysable esterase activity in Delhi population was less as compared to the Guntur population. Resistance associated esterases in Delhi population were inhibited by pre-treatment with dihydrodillapiole. The esterase level in insect was instantly reduced initially, sustained for about 3 h and equilibrated at 4 h post treatment. The esterase activity of Guntur population was increased to 1.28 μmoles/mg/min at 2 h post treatment and subsequently reduced to lower than 0.70 μmoles at 4-12 h post treatment. The variation in esterase activity is suggestive of its homeostatic regulation in test populations. Dihydrodillapiole thus caused significant reduction of resistance in S. litura to cypermethrin, lambda cyhalothrin and profenophos.     

Structure–Activity Relationships of Herbicidal Aryltriazolinones

A series of substituted aryltriazolinones, known to inhibit protoporphyrinogen oxidase, were prepared and their structure–activity requirements at positions 4 and 5 of the aromatic ring investigated. A QSAR equation obtained for substituents at the 5 position identified the hydrophobicity term π and the Sterimol minimum width B₁ as the two parameters affecting in-vitro biological activity. Greenhouse pre-emergence activity correlated with in-vitro activity and the hydrophobicity term π of the substituent at that position. It was found that the phenoxy-4-oxyacetate group at aromatic position 5 was an outlier and had to be considered separately. SAR analysis of substituents at aromatic position 4 revealed that two different models were required to explain all observed substituent effects. In the first model, where the 5 position was occupied by hydrogen, the 4-chlorobenzyloxy group at aromatic position 4 gave the best compound. The second model, where the 5 position of the aromatic ring was occupied by a group other than hydrogen, resulted in a QSAR equation, previously derived, which links substituent effects at position 4 with π and with the electronic para inductive term F_p. In this model the chloro group provides optimum biological activity. The need to separate the aryltriazolinone herbicides into several different classes in order to explain their substituent effects at aromatic positions 4 and 5 could be rationalized if more than one binding conformation, within the same binding site, is possible. © 1997 SCI     

几种有机磷杀蚜——螨剂的室内毒力试验

应用液剂定量直接喷布法,对两种蚜虫、棉红蜘蛛、家蝇进行多次室内速效触杀毒力测定,以及在温室进行的棉红蜘蛛残效测定初步表明:(1)乐果对两种蚜虫和棉红蜘蛛的速效触杀毒力均接近或超过 E-1059;对家蝇具有高度的触杀毒力。(2)甲基异 G-1059不论对两种蚜虫或棉红蜘蛛都表现很高的杀虫毒力。(3)甲基 K-1059和马拉硫磷对两种蚜虫和棉红蜘蛛毒力的都不够强。(4)三硫磷对棉红蜘蛛成虫也具有高度的触杀毒力,粗制原油的毒力强度接近 E-1059.三硫磷对棉红蜘蛛的残效相当好。(5)AC-3741对棉红蜘蛛成虫的速效触杀毒力也相当强,杀螨毒力强度约为 E-1059的一半;但对两种蚜虫的毒力不够强。     

Communication to the Editor Degradation of Bromoxynil,Ioxynil, Dichlobenil and their Mixtures by Agrobacterium radiobacter 8/4

Degradation of three benzonitrile herbicides, bromoxynil (3,5-dibromo-4-hydroxybenzonitrile), ioxynil (3,5-diiodo-4-hydroxybenzonitrile), dichlobenil (2,6-dichlorobenzonitrile), and their mixtures by the soil micro-organism Agrobacterium radiobacter 8/4 was studied in batch cultures. Bromoxynil was found to be most rapidly degraded, while dichlobenil had the lowest toxicity to our strain. All transformations of studied benzonitriles were performed by the nitrile hydratase which has been shown to act on a broad range of substituted aromatic nitriles. © 1997 SCI.     

Toxicity of chlordimeform and amitraz to the egyptian cotton leafworm (Spodoptera littoralis) and the tobacco budworm (Heliothis virescens)

The relative toxicity (μg a.i. g^?1 body wt) of the formamidine insecticide chlordimeform (CDM) and the triazapentadiene insecticide amitraz was examined in two species of noctuid moth Spodoptera littoralis and Heliothis virescens. When applied topically, there was an unexpected and marked difference in the toxicity of CDM base and its hydrochloride to adults of both species, the salt being appreciably more toxic. For H. virescens at least, this difference in toxicity could not be explained by differences in penetration. This trend was reversed for larval instars of S. littoralis; while there was relatively little difference in the toxicity of the base to adult and larval stages, the salt was at least 1000-fold more toxic to adults than to larvae. N¹-Demethylchlordimeform (DCDM) was the only metabolite of CDM to show biological activity against either species, but was much less toxic than the parent compound. Amitraz was far less toxic than either CDM or DCDM; like the CDM salt, it appeared to be more toxic to adult than larval stages of S. littoralis. Application of piperonyl butoxide significantly increased the toxicity of the CDM salt, DCDM and amitraz to adult H. virescens, the synergist being particularly effective with DCDM and amitraz. In contrast, piperonyl butoxide had no significant effect on the toxicity of DCDM, and slightly antagonised the toxicity of DCDM to fourth-instar larvae of S. littoralis.     

棉铃虫核多角体病毒的生产方法及其在生物防治中的应用

本文是报道棉铃虫Heliothis armigera核多角体病毒(NPV)的生产方法及其在棉田应用的试验研究结果。NPV用棉铃虫幼虫生产。从虫卵接种开始,用人工饲料饲养棉铃虫幼虫,到四龄用病毒感染,六天后收集病死虫,病毒致死率80～85%,单虫含量4～6×10~9PIB。由棉饼粉、粗棉油等配制成诱饵加低剂量西维因作病毒增效剂与NPV混用,显著提高病毒的防治效果。四年田间试验表明,NPV杀虫剂防治棉铃虫的效果相当于或优于常用高效化学农药。1979年开展了大面积飞机微量喷雾PVN杀虫剂的试验,也取得了比较好的防治效果。     

Use of diatomaceous earth for the management of stored-product pests

Diatomaceous earth (DE) is almost pure amorphous silicon dioxide, made up of fossilised diatoms; it acts as an insecticide by absorption of epicuticular lipids and fatty acids, leading to desiccation in arthropods. Numerous DE formulations have been attempted for the management of stored-product pests with good results. DE is persistent in its action, poses few or no pest resistance problems, and it leaves no residue. The efficacy of DE is affected by factors such as: its provenance, temperature, humidity and characteristics of target pests and substrate. Application of DE at currently recommended doses causes changes in bulk density of the grain; however, the use of enhanced DE formulations provides control at much lower doses. Therefore, new formulations of DEs usually include other low toxicity insecticides.